WO2019054480A1 - 光熱変換層、当該光熱変換層を用いたドナーシート、およびそれらの製造方法 - Google Patents

光熱変換層、当該光熱変換層を用いたドナーシート、およびそれらの製造方法 Download PDF

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WO2019054480A1
WO2019054480A1 PCT/JP2018/034176 JP2018034176W WO2019054480A1 WO 2019054480 A1 WO2019054480 A1 WO 2019054480A1 JP 2018034176 W JP2018034176 W JP 2018034176W WO 2019054480 A1 WO2019054480 A1 WO 2019054480A1
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Prior art keywords
tungsten oxide
conversion layer
composite tungsten
oxide fine
light
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PCT/JP2018/034176
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English (en)
French (fr)
Japanese (ja)
Inventor
裕史 常松
長南　武
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住友金属鉱山株式会社
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Application filed by 住友金属鉱山株式会社 filed Critical 住友金属鉱山株式会社
Priority to CN201880059486.2A priority Critical patent/CN111095047B/zh
Priority to CA3086138A priority patent/CA3086138A1/en
Priority to AU2018331911A priority patent/AU2018331911B2/en
Priority to KR1020207004245A priority patent/KR102676075B1/ko
Priority to EP18856184.9A priority patent/EP3683604A4/en
Priority to JP2019542307A priority patent/JP7156290B2/ja
Priority to US16/647,600 priority patent/US11912054B2/en
Publication of WO2019054480A1 publication Critical patent/WO2019054480A1/ja
Priority to IL273260A priority patent/IL273260A/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M5/00—Duplicating or marking methods; Sheet materials for use therein
    • B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
    • B41M5/40—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography
    • B41M5/46—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used characterised by the base backcoat, intermediate, or covering layers, e.g. for thermal transfer dye-donor or dye-receiver sheets; Heat, radiation filtering or absorbing means or layers; combined with other image registration layers or compositions; Special originals for reproduction by thermography characterised by the light-to-heat converting means; characterised by the heat or radiation filtering or absorbing means or layers
    • B41M5/465—Infrared radiation-absorbing materials, e.g. dyes, metals, silicates, C black
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/06—Interconnection of layers permitting easy separation
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B5/00—Optical elements other than lenses
    • G02B5/20—Filters
    • G02B5/22—Absorbing filters
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H10K50/11—OLEDs or polymer light-emitting diodes [PLED] characterised by the electroluminescent [EL] layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
    • B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
    • B41M2205/00—Printing methods or features related to printing methods; Location or type of the layers
    • B41M2205/06—Printing methods or features related to printing methods; Location or type of the layers relating to melt (thermal) mass transfer
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K50/00—Organic light-emitting devices
    • H10K50/10—OLEDs or polymer light-emitting diodes [PLED]
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K71/00—Manufacture or treatment specially adapted for the organic devices covered by this subclass
    • H10K71/10—Deposition of organic active material
    • H10K71/18—Deposition of organic active material using non-liquid printing techniques, e.g. thermal transfer printing from a donor sheet

Definitions

  • the present invention relates to a light-to-heat conversion layer, a donor sheet using the light-to-heat conversion layer, and a method for producing them.
  • the light-to-heat conversion layer is a layer having a characteristic that a portion irradiated with infrared rays or near infrared rays generates heat, and a portion not irradiated does not generate heat. Therefore, by irradiating the light-to-heat conversion layer with an infrared laser or a near-infrared laser, it becomes possible to generate heat only at a desired location, so that it can be used in a wide range of fields such as electronics, medicine, agriculture, and machinery. Application is expected. However, as an urgent application, the application as a donor sheet used for manufacture of an organic electroluminescent element in the electronics field can be considered. Therefore, the light-to-heat conversion layer will be described below by taking the case of the donor sheet as an example.
  • a metal mask method As a method of forming an organic electroluminescent element on a substrate, a metal mask method, a laser transfer method, an inkjet method, etc. have been studied.
  • the metal mask method is difficult to cope with the large area such as next-generation large display devices, and the ink jet method has many technical issues for application, so the laser transfer method is a process for large displays. Is expected to become mainstream.
  • a method of forming a film using a film called a donor sheet is the mainstream.
  • a donor sheet for example, a film substrate on which a layer called light-to-heat conversion (LTHC: Light To Heat Conversion) layer is absorbed and a layer of an organic compound having an electroluminescence property as a transferred layer is formed.
  • LTHC Light To Heat Conversion
  • Patent Document 1 discloses dyes that absorb light in the infrared region, organic and inorganic absorption materials such as carbon black, metals, metal oxides or metal sulfides, and other known pigments and absorbers.
  • Patent Document 2 discloses dyes, pigments, metals, metal compounds, metal films and the like.
  • Patent Document 3 discloses black aluminum.
  • Patent Document 4 discloses carbon black, graphite and an infrared dye.
  • an organic electroluminescent device is formed by a laser transfer method
  • laser light is irradiated to a desired location in the light-to-heat conversion layer of the donor sheet to transfer the organic electroluminescent device included in the donor sheet. It can be carried out.
  • the organic electroluminescent element at the laser irradiation location is not properly transferred, which causes dots not to be lit when it becomes a display device. . Therefore, in order to improve the yield, it is conceivable to detect a donor sheet containing a defect by visual inspection or a visible light sensor or the like before laser transfer.
  • the present applicant has patented a light-to-heat conversion layer having visible light transparency comprising composite tungsten oxide fine particles, which are near-infrared absorption particles, and a binder component, and a donor sheet using the light-to-heat conversion layer. It is disclosed as Document 5.
  • the light-to-heat conversion layer having visible light transmission disclosed by the present applicant and the donor sheet using the light-to-heat conversion layer enable visual detection or defect detection by a visible light sensor or the like.
  • the requirement for the transfer accuracy of the organic electroluminescent device included in the donor sheet by the irradiation of the laser light has been remarkably increased.
  • the visible light transmissivity containing the composite tungsten oxide fine particles which is the near-infrared absorbing particle according to the prior art disclosed in Patent Document 5 described above, and the binder component It has been found that it may be difficult to transfer the organic electroluminescent element by irradiation of the laser light with high accuracy in the light-heat conversion layer and the donor sheet using the light-heat conversion layer.
  • the present invention has been made under the above-mentioned circumstances, and the problem to be solved is an organic electroluminescent device having visible light transparency, sufficient infrared absorption characteristics, and irradiation with laser light.
  • Light-to-heat conversion layer that can improve the transfer accuracy of the light-emitting layer and can be applied to a wide range of fields such as electronics, medical, agriculture, machinery, etc., donor sheets using the light-to-heat conversion layer, and methods for producing them And to provide.
  • the present inventors conducted research. And, in the light-to-heat conversion layer having visible light transmissivity containing the composite tungsten oxide fine particles which is the near-infrared absorbing particle according to the prior art disclosed in Patent Document 5 and the binder component, It was found that haze caused by the dispersed composite tungsten oxide fine particles was generated. Then, it was found that the laser light irradiated with the haze was scattered, and only the portion irradiated with the infrared light should be the heat generation position, and the accuracy of the heat generation position was lowered. As a result, it was thought that the improvement of the transfer accuracy of the organic electroluminescent element was inhibited.
  • the present inventors studied a method of reducing the haze caused by the composite tungsten oxide fine particles dispersed in the binder component. Then, in the composite tungsten oxide fine particles, in the composite tungsten oxide fine particles which are the infrared light absorbing material fine particles, the crystals contained are made hexagonal, the values of the a axis and the c axis in their lattice constants are 7.3850 ⁇ for the a axis It is considered that the crystallinity is enhanced with the above-described 7.4186 ⁇ or less and the c-axis being 7.5600 ⁇ or more and 7.6240 ⁇ or less, and the particle diameter of the fine particles is 100 nm or less.
  • the composite tungsten oxide fine particles having the predetermined lattice constant are excellent in infrared absorption characteristics, and exhibit sufficient infrared absorption characteristics even with a content smaller than that of the composite tungsten oxide fine particles according to the prior art.
  • the present inventors have used the composite tungsten oxide fine particles having the predetermined crystal structure, thereby securing the visible light transmittance and the sufficient infrared absorption characteristics, and oxidizing the composite tungsten in the light-heat conversion layer. It was conceived that the haze could be reduced by reducing the content of the fine particles. Then, it has been found that the light-to-heat conversion layer containing the composite tungsten oxide fine particles having the predetermined crystal structure has a highly accurate heat generation position and generates heat only at the portion irradiated with the infrared light.
  • the light-to-heat conversion layer containing the composite tungsten oxide fine particles having the predetermined crystal structure is applicable to a wide range of fields such as electronics, medicine, agriculture, machinery, etc., and the light-to-heat conversion layer is used.
  • the present invention was completed on the assumption that the transfer accuracy of the organic electroluminescent element can be improved.
  • the first invention for solving the above-mentioned problems is: Contains infrared absorbing particles and a binder component,
  • the infrared absorbing particle is a composite tungsten oxide fine particle having a hexagonal crystal structure
  • the lattice constant of the composite tungsten oxide fine particles is 7.3850 ⁇ or more and 7.4186 ⁇ or less for the a axis and 7.5600 ⁇ or more and 7.6240 ⁇ or less for the c axis.
  • the light-to-heat conversion layer is characterized in that the particle diameter of the composite tungsten oxide fine particles is 100 nm or less.
  • the second invention is The photothermal conversion according to the first invention is characterized in that the lattice constant of the composite tungsten oxide fine particle is that the a-axis is 7.4031 ⁇ or more and 7.4111 ⁇ or less and the c-axis is 7.5891 ⁇ or more and 7.6240 ⁇ or less It is a layer.
  • the third invention is The particle diameter of the composite tungsten oxide fine particles is 10 nm or more and 100 nm or less.
  • the fourth invention is The light-to-heat conversion layer according to any one of the first to third inventions, wherein a crystallite diameter of the composite tungsten oxide fine particles is 10 nm or more and 100 nm or less.
  • the fifth invention is The composite tungsten oxide fine particles have a general formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir) , Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, Tl, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, Br, Te, Ti Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, and Yb, W being tungsten, O being oxygen, 0.001 ⁇ x / y
  • the light-to-heat conversion layer according to any one of the first to fourth inventions, which is a composite tungsten oxide fine particle represented by ⁇ 1, 2.0 ⁇ z / y ⁇ 3.0).
  • the sixth invention is The photothermal conversion layer according to the fifth invention, wherein the M element is one or more elements selected from Cs and Rb.
  • the seventh invention is At least a part of the surface of the composite tungsten oxide fine particles is covered with a surface covering film containing at least one or more elements selected from Si, Ti, Zr, and Al. It is a light-to-heat conversion layer according to any one of the first to sixth inventions.
  • the eighth invention is The light-to-heat conversion layer according to the seventh invention, wherein the surface coating film contains an oxygen atom.
  • the ninth invention is The thickness of the said photothermal conversion layer is 5 micrometers or less, It is a photothermal conversion layer in any one of the 1st-8th invention characterized by the above-mentioned.
  • the tenth invention is A dry cured product of an ink applied on a substrate,
  • the eleventh invention is A donor sheet comprising the light-to-heat conversion layer according to any of the first to tenth inventions, a film substrate, and a transfer layer.
  • the twelfth invention is A method for producing a light-to-heat conversion layer comprising infrared absorbing particles and a binder component,
  • the infrared absorbing particle is a composite tungsten oxide fine particle having a hexagonal crystal structure
  • the composite tungsten oxide fine particles are manufactured so that the lattice constant is in the range of 7.3850 ⁇ to 7.4186 ⁇ in the a axis and 7.5600 ⁇ to 7.6240 ⁇ in the c axis.
  • It is a manufacturing method of the photothermal conversion layer characterized by performing a grinding / dispersing treatment process which makes an average particle diameter 100 nm or less, maintaining the range of the lattice constant in the composite tungsten oxide fine particles.
  • the fourteenth invention is The method for producing a photothermal conversion layer according to the thirteenth invention, wherein the M element is one or more elements selected from Cs and Rb.
  • the fifteenth invention is At least a part of the surface of the composite tungsten oxide fine particles is covered with a surface covering film containing at least one or more elements selected from Si, Ti, Zr, and Al. It is a manufacturing method of the photothermal conversion layer in any one of 14th invention.
  • the sixteenth invention is It is a manufacturing method of the light-to-heat conversion layer according to the fifteenth invention, wherein the surface coating film contains an oxygen atom.
  • the seventeenth invention is The thickness of the said light-to-heat conversion layer shall be 5 micrometers or less, It is a manufacturing method of the light-to-heat conversion layer in any one of the 12th to 16th invention characterized by the above-mentioned.
  • the light-to-heat conversion layer according to the present invention can be applied to a wide range of fields such as electronics, medical care, agriculture, machinery, etc., since only the portion irradiated with infrared light generates heat with high precision heat generation position.
  • the transfer accuracy of the organic electroluminescent device can be improved by using a donor sheet using the light-to-heat conversion layer.
  • the light-to-heat conversion layer according to the present invention is a light-to-heat conversion layer containing composite tungsten oxide fine particles having a predetermined configuration as an infrared ray absorbing component.
  • the donor sheet according to the present invention has a light-to-heat conversion layer 22 including infrared absorbing particles 221 on one surface 21A of the film substrate 21 as shown in FIG. It has the structure which laminated
  • Composite tungsten oxide fine particles The composite tungsten oxide fine particles according to the present invention and a composite tungsten oxide fine particle dispersion used for producing a light-to-heat conversion layer described later containing the composite tungsten oxide fine particles, [A] Properties of composite tungsten oxide fine particles, [b] Synthesis method of composite tungsten oxide fine particles, [c] Composite tungsten oxide fine particle dispersion, [d] Composite tungsten oxide fine particle dispersion dry treatment method It explains in order.
  • the composite tungsten oxide fine particles according to the present invention are composite tungsten oxide fine particles having infrared absorption characteristics and including a hexagonal crystal structure shown in FIG.
  • the lattice constant of the composite tungsten oxide fine particles of the present invention is such that the a axis is 7.3850 ⁇ or more and 7.4186 ⁇ or less and the c axis is 7.5600 ⁇ or more and 7.6240 ⁇ or less.
  • the composite tungsten oxide fine particles according to the present invention have a particle diameter of 100 nm or less.
  • shaft) is 1.0221 or more and 1.0289 or less.
  • the composite tungsten oxide fine particles according to the present invention have a tetragonal or cubic tungsten bronze structure other than hexagonal crystals, but any structure is effective as an infrared absorbing material It is.
  • the absorption position in the infrared region tends to change depending on the crystal structure of the composite tungsten oxide fine particles. That is, the absorption position in the infrared region tends to move to the longer wavelength side when tetragonal than cubic, and to move further to the longer wavelength than tetragonal when it is hexagonal.
  • absorption of light in the visible light region is the least hexagonal and secondly tetragonal, and the cubic is the largest among them.
  • hexagonal tungsten bronze for applications in which light in the visible light region is more transmitted and light in the infrared region is more absorbed.
  • the composite tungsten oxide particles have a hexagonal crystal structure, the transmittance of the particles in the visible light region is improved, and the absorption in the near infrared region is improved.
  • this hexagonal crystal structure six octahedra formed of WO 6 units are assembled to form a hexagonal void (tunnel), and the M element is disposed in the void to form one unit. , And a large number of units of one unit are assembled to form a hexagonal crystal structure.
  • a unit structure 11 (WO 6 units shown in FIG. 2 It is only necessary that six octahedrons are gathered to form a hexagonal void, and the void has a structure in which the element M12 is disposed.
  • the absorption in the infrared region is improved.
  • the hexagonal crystal is formed, and specifically, one or more selected from Cs, Rb, K, Tl, Ba, and In are added.
  • hexagonal crystals are easily formed, which is preferable. Furthermore, in the composite tungsten oxide fine particles added with one or more types selected from Cs and Rb among these M elements having large ionic radius, it is possible to achieve both the absorption in the infrared region and the transmission in the visible light region. When two or more kinds of M elements are selected, one of them is selected from Cs, Rb, K, Tl, Ba, and In, and the rest is selected from one or more elements constituting the M element. It may also be hexagonal.
  • the lattice constant thereof is preferably 7.4031 ⁇ or more and 7.4186 ⁇ or less for the a axis and 7.5750 ⁇ or more and 7.6240 ⁇ or less for the c axis
  • the a-axis is 7.4031 ⁇ or more and 7.4111 ⁇ or less
  • the c-axis is 7.5891 ⁇ or more and 7.6240 ⁇ or less.
  • the lattice constant thereof is preferably 7.3850 ⁇ to 7.3950 ⁇ for the a axis and 7.5600 ⁇ to 7.5700 ⁇ for the c axis.
  • the lattice constant is that the a axis is 7.3850 ⁇ or more and 7.4186 ⁇ or less and the c axis is 7.5600 ⁇ or more and 7.6240 ⁇ or less preferable.
  • the M element is not limited to the above Cs and Rb. Even if the M element is an element other than Cs and Rb, it may be present as an added M element in a hexagonal gap formed of a WO 6 unit.
  • Typical examples include Cs 0.33 WO 3 , Cs 0.03 Rb 0.30 WO 3 , Rb 0.33 WO 3 , K 0.33 WO 3 , Ba 0.33 WO 3 and the like. .
  • the inventors of the present invention conducted researches on measures for further improving the infrared absorption function of the composite tungsten oxide fine particles, and conceived of a configuration for further increasing the amount of free electrons contained. That is, as a measure to increase the amount of free electrons, mechanical processing is applied to the composite tungsten oxide fine particles to give appropriate distortion and deformation to the contained hexagonal crystals. In the hexagonal crystal to which the appropriate strain or deformation is given, it is considered that the overlapping state of the electron orbits in the atoms constituting the crystallite structure changes, and the amount of free electrons increases.
  • the present inventors manufacture a composite tungsten oxide fine particle dispersion liquid from particles of the composite tungsten oxide formed in the firing step of "a synthesis method of composite tungsten oxide fine particles" described later.
  • the particles of the composite tungsten oxide are crushed under predetermined conditions to impart distortion or deformation to the crystal structure to increase the amount of free electrons, and the infrared absorption function of the composite tungsten oxide fine particles, That is, research was made to further improve the light-to-heat conversion function.
  • generated through the baking process were examined paying attention to each particle
  • the inventors of the present invention who have obtained the above-mentioned findings further measure distortion and deformation of the crystal structure of the fine particle by measuring the a-axis and c-axis which are lattice constants in the crystal structure of the complex tungsten oxide fine particle.
  • the optical properties of the particles were studied while grasping the degree.
  • the fine particles have a wavelength of 350 nm to We have found that it is an infrared-absorbing material fine particle having a maximum value in the range of 600 nm, a transmittance of light having a minimum value in the range of wavelength 800 nm to 2100 nm, and exhibiting an excellent infrared absorption effect.
  • hexagonal composite tungsten oxide fine particles having a-axis of 7.3850 ⁇ or more and 7.4186 ⁇ or less and c-axis of 7.5600 ⁇ or more and 7.6240 ⁇ or less according to the present invention It was also found that when the value of x / y indicating the addition amount is in the range of 0.20 ⁇ x / y ⁇ 0.37, a particularly excellent infrared absorption effect is exhibited.
  • the composite tungsten oxide fine particles as the infrared light absorbing material fine particles are preferably single crystals in which the volume ratio of the amorphous phase is 50% or less. If the composite tungsten oxide fine particles are a single crystal having a volume ratio of 50% or less of the amorphous phase, the crystallite diameter can be 10 nm or more and 100 nm or less while maintaining the lattice constant within the above-described predetermined range, It is considered that excellent optical properties can be exhibited.
  • the composite tungsten oxide fine particles are a single crystal is confirmed because no grain boundaries are observed inside each fine particle in an electron microscope image by a transmission electron microscope etc., and only a uniform checkered pattern is observed. can do.
  • the volume ratio of the amorphous phase is 50% or less, similarly to the transmission electron microscope image, a uniform checkered pattern is observed throughout the fine particles, and a portion where the checkered pattern is unclear is almost observed It can be confirmed from not being done.
  • the amorphous phase is often present at the outer peripheral portion of each particle, the volume ratio of the amorphous phase can often be calculated by focusing on the outer peripheral portion of each particle.
  • the composite tungsten oxide oxide has a thickness of 10% or less of the particle diameter.
  • the volume ratio of the amorphous phase in the fine particles is 50% or less.
  • the composite tungsten oxide fine particles are dispersed in a matrix of a solid medium such as a resin constituting the light-to-heat conversion layer which is a composite tungsten oxide fine particle dispersion, the dispersed composite tungsten oxide fine particles If the value obtained by subtracting the crystallite size from the average particle size is 20% or less of the average particle size, it can be said that the composite tungsten oxide fine particles are a single crystal having a volume ratio of 50% or less of the amorphous phase.
  • the composite tungsten oxide such that the value obtained by subtracting the crystallite diameter from the average particle diameter of the composite tungsten oxide fine particles dispersed in the light-to-heat conversion layer is 20% or less of the value of the average particle diameter. It is preferable to appropriately adjust the synthesis process, the pulverization process, and the dispersion process of the fine particles according to the manufacturing equipment.
  • the measurement of the crystal structure and lattice constant of the composite tungsten oxide fine particles is carried out by using X-ray diffraction method for the composite tungsten oxide fine particles obtained by removing the solvent of the composite tungsten oxide fine particle dispersion described later.
  • the a-axis length and the c-axis length can be calculated as lattice constants by specifying the crystal structure contained and using the Rietveld method.
  • the composite tungsten oxide fine particles according to the present invention have a particle size of 100 nm or less. And from the viewpoint of exhibiting more excellent infrared absorption characteristics, the particle diameter is preferably 10 nm or more and 100 nm or less, more preferably 10 nm or more and 80 nm or less, and still more preferably 10 nm or more and 60 nm or less. If the particle diameter is in the range of 10 nm to 60 nm, the most excellent infrared absorption characteristics are exhibited.
  • the particle diameter is the value of the diameter of each composite tungsten oxide fine particle not aggregated, and is the particle diameter of the composite tungsten oxide fine particle contained in the light-to-heat conversion layer described later. On the other hand, the said particle diameter does not contain the diameter of the aggregate of composite tungsten oxide fine particles, and is different from the dispersed particle diameter.
  • the average particle size is calculated from an electron microscope image of a light-to-heat conversion layer described later.
  • the average particle diameter of the composite tungsten oxide fine particles contained in the light-to-heat conversion layer is the particle diameter of 100 composite tungsten oxide fine particles from the transmission electron microscope image of the exfoliated sample of the light-to-heat conversion layer It can measure by measuring using a processing apparatus and calculating the average value. At this time, when the composite tungsten oxide fine particles form an aggregate, the particle diameter is measured for each single particle constituting the aggregate. Therefore, the diameter of the aggregate is not included.
  • a microtome, a cross section polisher, a focused ion beam (FIB) apparatus or the like can be used for cross-sectional processing for taking out the exfoliated sample.
  • the average particle size of the composite tungsten oxide fine particles contained in the light-to-heat conversion layer is the average value of the particle sizes of the composite tungsten oxide fine particles dispersed in the solid medium which is the matrix.
  • the crystallite diameter of the composite tungsten oxide fine particles is preferably 10 nm to 100 nm, more preferably 10 nm to 80 nm, and still more preferably 10 nm to 60 nm. . If the crystallite diameter is in the range of 10 nm to 60 nm, the most excellent infrared absorption characteristics are exhibited.
  • the lattice constant, the crystallite diameter and the particle diameter of the composite tungsten oxide fine particles contained in the composite tungsten oxide fine particle dispersion obtained after the pulverization treatment, the pulverization treatment, or the dispersion treatment described later The composite tungsten oxide fine particles obtained by removing the volatile component from the fine particle dispersion and the composite tungsten oxide fine particles contained in the light-to-heat conversion layer obtained from the composite tungsten oxide fine particle dispersion are also maintained. As a result, the effect of the present invention is exhibited also in the light-to-heat conversion layer containing the composite tungsten oxide fine particle dispersion or the composite tungsten oxide fine particle according to the present invention.
  • the composite tungsten oxide fine particles according to the present invention have a general formula MxWyOz (where M is H, He, alkali metal, alkaline earth metal, rare earth element, Mg, Zr, Cr) Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Zn, Cd, Al, Ga, In, T1, Si, Ge, Sn, Pb, Sb, B, F , P, S, Se, Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, Yb, one or more elements, W is tungsten, O is preferably a composite tungsten oxide fine particle represented by oxygen, 0.001 ⁇ x / y ⁇ 1, 2.0 ⁇ z / y ⁇ 3.0).
  • the composite tungsten oxide fine particles represented by the general formula MxWyOz will be described.
  • the M element, x, y, z and the crystal structure thereof in the general formula MxWyOz are closely related to the free electron density of the composite tungsten oxide fine particles, and greatly influence the infrared absorption characteristics.
  • tungsten trioxide has low infrared absorption characteristics because no effective free electrons exist.
  • the present inventors indicate that the tungsten oxide can be converted into the M element (wherein the M element is H, He, an alkali metal, an alkaline earth metal, a rare earth element, Mg, Zr, Cr, Mn, Fe, Ru, Co, Rh, Ir, Ni, Pd, Pt, Cu, Ag, Au, Zn, Cd, Al, Ga, In, T1, Si, Ge, Sn, Pb, Sb, B, F, P, S, Se, At least one element selected from Br, Te, Ti, Nb, V, Mo, Ta, Re, Be, Hf, Os, Bi, I, Yb) to form a composite tungsten oxide
  • free electrons are generated in the composite tungsten oxide, and absorption characteristics derived from free electrons appear in the infrared region, and become effective as an infrared absorbing material in the vicinity of a wavelength of
  • the M element is preferably Cs, Rb, K, Tl, Ba, or In.
  • the M element is Cs or Rb
  • the composite tungsten oxide can easily have a hexagonal crystal structure.
  • visible light is transmitted and infrared rays are absorbed and absorbed, it has also been found that it is particularly preferable for the reason described later.
  • M elements are selected, one of them is selected from Cs, Rb, K, Tl, Ba, and In, and the rest is selected from one or more elements constituting the M element. Also, it may be hexagonal.
  • the present inventors' knowledge about the value of x which shows the addition amount of M element is demonstrated. If the value of x / y is 0.001 or more, a sufficient amount of free electrons can be generated to obtain the desired infrared absorption characteristics. The amount of free electrons supplied increases as the amount of M element added increases, and the infrared absorption characteristics also increase. Moreover, if the value of x / y is 1 or less, generation of an impurity phase in the composite tungsten fine particles can be avoided, which is preferable.
  • the present inventors' knowledge about the value of z which shows control of oxygen amount is demonstrated.
  • the value of z / y is preferably 2.0 ⁇ z / y ⁇ 3.0, more preferably 2.2 ⁇ z / y ⁇ 3. It is 0, more preferably 2.6 ⁇ z / y ⁇ 3.0, and most preferably 2.7 ⁇ z / y ⁇ 3.0. If the value of z / y is 2.0 or more, it is possible to avoid the appearance of the crystal phase of WO 2 other than the purpose in the composite tungsten oxide, and it is possible to obtain chemical stability as a material.
  • At least a part of the surface of the composite tungsten oxide fine particles is selected from silicon, zirconium, titanium and aluminum in order to improve the weather resistance of the composite tungsten oxide fine particles It is also preferable to coat with a surface coating film containing one or more elements. These surface coating films are basically transparent, and their addition does not reduce the visible light transmittance.
  • the coating method is not particularly limited, it is possible to coat the surface of the composite tungsten oxide particles by adding an alkoxide of a metal containing the above element to a solution in which the composite tungsten oxide particles are dispersed. In this case, the surface coating film contains oxygen atoms, but it is more preferable that the surface coating film is made of an oxide.
  • the lattice constant, particle diameter and crystallite diameter of the composite tungsten oxide fine particles described above in detail can be controlled by predetermined manufacturing conditions. Specifically, in the thermal plasma method and solid phase reaction method described later, the temperature (sintering temperature) at which the fine particles are formed, the formation time (sintering time), the formation atmosphere (sintering atmosphere) Control can be performed by appropriate setting of manufacturing conditions such as form, annealing after formation, doping with an impurity element, and the like.
  • Thermal Plasma Method The thermal plasma method will be described in the order of (i) raw materials used for the thermal plasma method, (ii) thermal plasma method and conditions thereof.
  • tungsten oxide fine particles according to the present invention are synthesized by the thermal plasma method, a mixed powder of a tungsten compound and an M element compound can be used as a raw material.
  • a tungsten compound tungstic acid (H 2 WO 4 ), ammonium tungstate, tungsten hexachloride, hydrate of tungsten obtained by hydrolysis after adding water to tungsten hexachloride dissolved in alcohol and then evaporating the solvent, It is preferable that it is 1 or more types chosen from.
  • the M element compound it is preferable to use one or more selected from oxides, hydroxides, nitrates, sulfates, chlorides, and carbonates of M elements.
  • the mixed powder of M element compound and a tungsten compound is obtained, and the said mixed powder can be made into the raw material of a thermal plasma method.
  • the raw material of the thermal plasma method in the case of obtaining the composite tungsten oxide obtained by 1st baking of the said mixed powder in the mixed gas atmosphere of inert gas independent or inert gas and reducing gas is obtained. It can also be done.
  • firing is performed in a mixed gas atmosphere of an inert gas and a reducing gas
  • the fired product in the first step is fired under an inert gas atmosphere.
  • the composite tungsten oxide obtained by the step firing can also be used as a raw material of the thermal plasma method.
  • thermal plasma method and conditions thereof any of direct current arc plasma, high frequency plasma, microwave plasma, low frequency alternating current plasma, or a superposition of these plasmas, or A plasma generated by an electrical method in which a magnetic field is applied to a direct current plasma, a plasma generated by irradiation of a high power laser, a plasma generated by a high power electron beam or an ion beam can be applied.
  • thermal plasma it is preferably a thermal plasma having a high temperature portion of 10000 to 15000 K, and in particular, a plasma capable of controlling the generation time of the fine particles.
  • the raw material supplied into the thermal plasma having the high temperature part evaporates instantaneously in the high temperature part. Then, the evaporated raw material is condensed in the process of reaching the plasma tail flame portion, and is rapidly solidified outside the plasma flame to generate composite tungsten oxide fine particles.
  • the synthesis method will be described with reference to FIG. 1 by taking a high frequency plasma reaction apparatus as an example.
  • a reaction system constituted by a water-cooled quartz double pipe and the inside of the reaction vessel 6 is evacuated to about 0.1 Pa (about 0.001 Torr) by an evacuation apparatus.
  • the inside of the reaction system is filled with argon gas to form an argon gas flow system at 1 atm.
  • any gas selected from argon gas, mixed gas of argon and helium (Ar-He mixed gas), or mixed gas of argon and nitrogen (Ar-N 2 mixed gas) as plasma gas in the reaction vessel Is introduced from the plasma gas supply nozzle 4 at a flow rate of 30 to 45 L / min.
  • Ar—He mixed gas is introduced from the sheath gas supply nozzle 3 at a flow rate of 60 to 70 L / min as a sheath gas flowing immediately outside the plasma region.
  • an alternating current is applied to the high frequency coil 2 to generate a thermal plasma 1 by a high frequency electromagnetic field (frequency 4 MHz). At this time, the high frequency power is set to 30 to 40 kW.
  • the mixed powder of the M element compound and the tungsten compound obtained by the above synthesis method from the powder supply nozzle 5 or the composite tungsten oxide is supplied from the gas supply device with an argon gas of 6 to 98 L / min as a carrier.
  • the gas is introduced into the thermal plasma at a supply rate of 25 to 50 g / min and reacted for a predetermined time.
  • the produced composite tungsten oxide fine particles pass through the suction pipe 7 and are deposited on the filter 8 and are collected.
  • the carrier gas flow rate and the raw material supply rate greatly affect the generation time of the particles. Therefore, it is preferable to set the carrier gas flow rate to 6 L / min to 9 L / min and the raw material supply rate to 25 to 50 g / min.
  • the plasma gas flow rate is preferable to set to 30 L / min to 45 L / min and the sheath gas flow rate to 60 L / min to 70 L / min.
  • the plasma gas has a function of maintaining a thermal plasma region having a high temperature portion of 10000 to 15000 K, and the sheath gas has a function of cooling the inner wall surface of the quartz torch in the reaction vessel to prevent melting of the quartz torch.
  • the flow rate of these gases is an important parameter for shape control of the plasma region.
  • the shape of the plasma region extends in the gas flow direction and the temperature gradient of the plasma tail becomes gentle, so the generation time of generated particles is extended and particles with good crystallinity are generated. become able to.
  • the composite tungsten oxide obtained by the thermal plasma method has a crystallite diameter exceeding 100 nm, or the composite tungsten oxide particle dispersion obtained from the composite tungsten oxide obtained by the thermal plasma method When the dispersed particle diameter of the tungsten oxide exceeds 200 nm, the pulverization / dispersion treatment described later can be performed.
  • the plasma conditions and the subsequent pulverization / dispersion treatment conditions are appropriately selected, and the particle diameter of the composite tungsten oxide, the crystallite diameter, and the a-axis length of the lattice constant
  • the effect of the present invention is exhibited by determining the pulverizing conditions (particulate conditions) to which the c-axis length can be imparted.
  • Solid Phase Reaction Method The solid phase reaction method will be described in the order of (i) raw materials used in the solid phase reaction method, (ii) firing in the solid phase reaction method and conditions thereof.
  • tungsten compound and an M element compound are used as a raw material.
  • Tungsten compounds are hydrolyzed by adding tungstic acid (H 2 WO 4 ), ammonium tungstate, tungsten hexachloride, tungsten hexachloride dissolved in alcohol to water by adding water, and then evaporating the solvent, the hydrate of tungsten, It is preferable that it is 1 or more types chosen from.
  • MxWyOz (wherein M is one or more elements selected from Cs, Rb, K, Tl, Ba, In), which is a more preferable embodiment, 0.001 ⁇ x / y ⁇ 1, 2.
  • M element compounds used for producing the raw material of the composite tungsten oxide fine particles shown by 0 ⁇ z / y ⁇ 3.0) include oxides, hydroxides, nitrates, sulfates, chlorides, and carbonates of M elements. It is preferable that it is 1 or more types chosen from,.
  • a compound containing one or more impurity elements selected from Si, Al, and Zr may be included as a raw material.
  • the impurity element compound does not react with the composite tungsten compound in the later firing step, and suppresses the crystal growth of the composite tungsten oxide to prevent the coarsening of the crystal.
  • the compound containing the impurity element is preferably at least one selected from oxides, hydroxides, nitrates, sulfates, chlorides, and carbonates, and colloidal silica and colloidal alumina having a particle diameter of 500 nm or less are particularly preferable. preferable.
  • the impurity element compound is contained as a raw material, the impurity element compound is wet mixed so as to be 0.5% by mass or less. Then, the obtained mixed liquid is dried to obtain a mixed powder of the M element compound and the tungsten compound, or a mixed powder of the M element compound and the tungsten compound containing the impurity element compound.
  • (Ii) Firing in the solid phase reaction method and conditions thereof A mixed powder of an M element compound and a tungsten compound produced by the wet mixing, or a mixed powder of an M element compound and an tungsten compound containing an impurity element compound
  • the firing is performed in one step under an atmosphere of active gas alone or a mixed gas of an inert gas and a reducing gas.
  • the firing temperature is preferably close to the temperature at which the composite tungsten oxide fine particles begin to crystallize, and specifically, the firing temperature is preferably 1000 ° C. or less, more preferably 800 ° C. or less, 800 ° C. or less 500 ° C. The above temperature range is more preferable.
  • the reducing gas is not particularly limited, but H 2 is preferable.
  • H 2 is used as the reducing gas, its concentration may be appropriately selected according to the calcination temperature and the amount of the starting material, and is not particularly limited. For example, it is 20% by volume or less, preferably 10% by volume or less, more preferably 7% by volume or less. If the concentration of the reducing gas is 20% by volume or less, it is possible to avoid the generation of WO 2 having no solar radiation absorbing function by rapid reduction.
  • the particle diameter, crystallite diameter, a-axis length and c-axis length of lattice constant of the composite tungsten oxide fine particles according to the present invention can be set to predetermined values by controlling the firing conditions.
  • tungsten trioxide may be used instead of the tungsten compound.
  • the present invention if the particle diameter, crystallite diameter, and a-axis length and c-axis length of lattice constant of composite tungsten oxide fine particles obtained through grinding and dispersion processing realize the range of the present invention, the present invention
  • the composite tungsten oxide fine particles according to the present invention and the photothermal conversion layer obtained from the dispersion thereof can realize excellent infrared absorption characteristics.
  • the composite tungsten oxide fine particles according to the present invention have a particle diameter of 100 nm or less.
  • a composite tungsten oxide fine particle dispersion liquid used for producing a light-to-heat conversion layer described later containing the composite tungsten oxide fine particles obtained in the above-described step will be described.
  • the composite tungsten oxide fine particle dispersion is selected from the composite tungsten oxide fine particles obtained by the above synthesis method, water, an organic solvent, a liquid resin, a liquid plasticizer for plastic, a polymer monomer, or a mixture of these.
  • the liquid medium of the mixed slurry and an appropriate amount of dispersing agent, coupling agent, surfactant and the like are pulverized and dispersed by a medium stirring mill.
  • the dispersed state of the fine particles in the solvent is good, and the dispersed particle diameter is 1 to 200 nm.
  • content of the composite tungsten oxide fine particle contained in this composite tungsten oxide fine particle dispersion liquid is 0.01 mass% or more and 80 mass% or less.
  • the liquid solvent used for the composite tungsten oxide fine particle dispersion is not particularly limited, and the coating conditions and the coating environment of the composite tungsten oxide fine particle dispersion, and the inorganic binder added appropriately It may be appropriately selected according to the resin binder and the like.
  • the liquid solvent is water, an organic solvent, a fat and oil, a liquid resin, a liquid plasticizer for a medium resin, a polymer monomer, or a mixture thereof.
  • alcohol solvents such as methanol, ethanol, 1-propanol, isopropanol, butanol, pentanol, benzyl alcohol and diacetone alcohol; ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isobutyl ketone, cyclohexanone and isophorone Solvents; Ester solvents such as 3-methyl-methoxy-propionate; ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol isopropyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol methyl ether acetate, propylene Glycol derivatives such as glycol ethyl ether acetate; , N- methyl formamide,
  • chlorobenzene can be used.
  • organic solvents dimethyl ketone, methyl ethyl ketone, methyl isobutyl ketone, toluene, propylene glycol monomethyl ether acetate, n-butyl acetate and the like are particularly preferable.
  • vegetable fats and oils are preferable.
  • vegetable oils include dry oils such as linseed oil, sunflower oil, soy sauce and eno oil, sesame oil, cottonseed oil, rapeseed oil, semi-dry oil such as soybean oil, rice bran oil and poppy seed oil, olive oil, palm oil, palm oil and dehydrated castor oil Etc. non-drying oil is used.
  • fatty acid monoester, ether etc. which carried out the ester reaction of the fatty acid of vegetable oil and monoalcohol directly are used.
  • the liquid plasticizer for example, a plasticizer that is a compound of a monohydric alcohol and an organic acid ester, an ester-based plasticizer such as a polyhydric alcohol organic acid ester compound, an organic phosphoric acid plasticizer, etc.
  • the plasticizer which is a phosphoric acid type is mentioned, and as for all, what is liquid at room temperature is preferable.
  • a plasticizer which is an ester compound synthesized from a polyhydric alcohol and a fatty acid is preferable.
  • the ester compound synthesized from polyhydric alcohol and fatty acid is not particularly limited.
  • glycol such as triethylene glycol, tetraethylene glycol, tripropylene glycol and the like, butyric acid, isobutyric acid, caproic acid, 2-ethylbutyric acid, heptylic acid
  • glycol ester compounds obtained by reaction with monobasic organic acids such as n-octylic acid, 2-ethylhexylic acid, pelargonic acid (n-nonylic acid) and decylic acid.
  • ester compounds of tetraethylene glycol and tripropylene glycol with the monobasic organic compounds and the like can also be mentioned.
  • fatty acid esters of triethylene glycol such as triethylene glycol dihexanate, triethylene glycol di-2-ethyl butyrate, triethylene glycol di-octanate, triethylene glycol di-2-ethyl hexanonate and the like are preferable. is there. Fatty acid esters of triethylene glycol are preferred.
  • a polymer monomer is a monomer which forms polymer
  • a methyl methacrylate monomer, an acrylate monomer, and a styrene resin are used as a preferable polymer monomer used by this invention.
  • a monomer etc. are mentioned.
  • liquid solvents described above can be used alone or in combination of two or more. Furthermore, if necessary, an acid or an alkali may be added to these liquid solvents to adjust the pH.
  • Dispersant to be used Furthermore, in order to further improve the dispersion stability of the composite tungsten oxide fine particles in the composite tungsten oxide fine particle dispersion and to avoid the coarsening of the dispersed particle size due to reaggregation, various kinds of The addition of dispersants, surfactants, coupling agents, etc. is also preferred.
  • the said dispersing agent, a coupling agent, and surfactant can be selected according to a use, it is preferable that it is group which has an amine, a hydroxyl group, a carboxyl group, or an epoxy group as a functional group.
  • These functional groups are adsorbed on the surface of the composite tungsten oxide fine particles to prevent aggregation, and have an effect of uniformly dispersing the composite tungsten oxide fine particles according to the present invention even in the infrared absorbing film. More desirable are polymeric dispersants having any of these functional groups in the molecule.
  • the method of dispersing the composite tungsten oxide fine particles in the dispersion liquid is not particularly limited as long as the fine particles can be uniformly dispersed in the dispersion liquid without aggregation.
  • pulverization * dispersion method the grinding * dispersion processing method using apparatuses, such as a bead mill, a ball mill, a sand mill, a paint shaker, an ultrasonic homogenizer, is mentioned, for example.
  • a medium media such as beads, balls, or Ottawa sand
  • a medium stirring mill such as a bead mill, a ball mill, a sand mill, or a paint shaker to grind and disperse.
  • pulverization of the composite tungsten oxide fine particles in the dispersion liquid by pulverization / dispersion processing using a medium stirring mill pulverization by the collision of the composite tungsten oxide fine particles or the collision of the medium with the fine particles also progresses
  • the composite tungsten oxide fine particles can be further micronized and dispersed (i.e., crushed and dispersed).
  • the crystallite diameter is preferably 10 nm or more and 100 nm or less, more preferably 10 nm or more and 80 nm or less, from the viewpoint of achieving excellent infrared absorption characteristics in the finely divided and dispersed composite tungsten oxide fine particles.
  • the grinding and dispersion treatment conditions are preferably adjusted to be 10 nm or more and 60 nm or less.
  • the composite tungsten oxide fine particles are dispersed in a plasticizer, it is also preferable to add an organic solvent having a boiling point of 120 ° C. or less, if desired.
  • organic solvent having a boiling point of 120 ° C. or less include toluene, methyl ethyl ketone, methyl isobutyl ketone, butyl acetate, isopropyl alcohol and ethanol.
  • any particle can be selected as long as it can uniformly disperse fine particles that exhibit an infrared absorption function at a boiling point of 120 ° C. or less.
  • the said organic solvent when added, it is preferable to implement a drying process after completion of dispersion, and to make the organic solvent which remains in a light-to-heat conversion layer 5 mass% or less. If the residual solvent of the light-to-heat conversion layer is 5% by mass or less, no bubbles are generated, and the appearance and the optical characteristics are well maintained.
  • the dispersed particle diameter in the composite tungsten oxide particle dispersion liquid of the composite tungsten oxide particles according to the present invention is preferably 200 nm or less, more preferably The dispersed particle diameter is 200 nm or less and 10 nm or more. This is because when the dispersed particle diameter of the composite tungsten oxide fine particles is 10 to 200 nm, the haze of the light-to-heat conversion layer described later can be reduced, and the light-to-heat conversion layer is used for transfer of organic electroluminescent elements etc. by irradiation of laser light. In this case, it is preferable from the viewpoint of improving the accuracy of the processing position and the like, and from the viewpoint of increasing the visible light transmittance.
  • Transparency can be ensured if the dispersed particle size of the fine particles is smaller than 200 nm, but if importance is placed on the transparency, the dispersed particle size is 150 nm or less, more preferably 100 nm or less. From the viewpoint of avoiding light scattering, it is preferable that the dispersed particle size be smaller. If the dispersed particle size is 10 nm or more, industrial production is easy.
  • the dispersed particle size of the composite tungsten oxide fine particles means the particle size of single particles of the composite tungsten oxide fine particles dispersed in the solvent, or the particle sizes of aggregated particles in which the composite tungsten oxide fine particles are aggregated. It can be measured by various commercially available particle size distribution analyzers. For example, a sample of the composite tungsten oxide fine particle dispersion can be collected, and the sample can be measured using ELS-8000 manufactured by Otsuka Electronics Co., Ltd. based on the principle of dynamic light scattering.
  • the composite tungsten oxide fine particle dispersion having a content of 0.01 to 80% by mass of the composite tungsten oxide fine particles obtained by the above synthesis method is excellent in liquid stability.
  • an appropriate liquid medium, dispersant, coupling agent or surfactant is selected, gelation of the dispersion or sedimentation of the particles does not occur for 6 months or more even when placed in a thermostatic chamber at a temperature of 40 ° C.
  • the dispersed particle size can be maintained in the range of 1 to 200 nm.
  • the dispersed particle diameter in the composite tungsten oxide fine particle dispersion may be different from the dispersed particle diameter in the light-to-heat conversion layer described later.
  • the composite tungsten oxide fine particles may be aggregated in the composite tungsten oxide fine particle dispersion. Then, when the light-to-heat conversion layer is manufactured using the composite tungsten oxide fine particle dispersion, aggregation of the composite tungsten oxide fine particles is resolved.
  • the composite tungsten oxide fine particle dispersion liquid can appropriately contain a binder described later.
  • a metal selected from the general formula XBm (where X is an alkaline earth element or a rare earth element containing yttrium) is added to the dispersion according to the present invention. It is also preferable to appropriately add an element, B, boron, a boride represented by 4 ⁇ m ⁇ 6.3, and infrared-absorbing particles such as ATO and ITO, as desired.
  • the addition ratio at this time may be appropriately selected according to the desired infrared absorption characteristics.
  • known inorganic pigments such as carbon black and red iron oxide and known organic pigments can be added.
  • the composite tungsten oxide fine particle dispersion may be added with a known ultraviolet absorber, a known infrared absorber of an organic substance, or a phosphorus-based color protection agent.
  • fine particles having the ability to emit far infrared radiation may be added.
  • metal oxides such as ZrO 2 , SiO 2 , TiO 2 , Al 2 O 3 , MnO 2 , MgO, Fe 2 O 3 , and CuO, carbides such as ZrC, SiC, and TiC, ZrN, Si 3 N 4 , and AlN And the like.
  • the composite tungsten oxide fine particle according to the present invention can be obtained by drying the composite tungsten oxide fine particle dispersion described above to remove the solvent.
  • drying equipment from the viewpoint that heating and / or depressurization is possible and mixing and recovery of the fine particles are easy, an air drier, a universal mixer, a ribbon mixer, a vacuum flow drier, a vibration flow drier Preferred are, but not limited to, machines, lyophilizers, ribocones, rotary kilns, spray dryers, Palcon dryers, and the like.
  • the light-to-heat conversion layer according to the present invention contains the composite tungsten oxide fine particles as infrared absorbing particles and the binder component, and the composite tungsten oxide fine particles are dispersed in the binder component.
  • the description will be made in the order of (1) binder component, (2) light-heat conversion layer, and the configuration thereof.
  • Binder Component The binder component is not particularly limited, and any binder component can be used. However, in the present invention, it is preferable to use a binder component excellent in visible light transmittance when it becomes solid, in order to provide a light-to-heat conversion layer having visible light transmittance. Moreover, when the laser light is irradiated to the light-to-heat conversion layer, the binder excellent in the light transmittance of the light in the infrared region, especially the near-infrared region, so that the laser light can be irradiated on the infrared absorbing particles contained in the light-to-heat conversion layer. It is preferred to use the components.
  • UV curable resin for example, UV curable resin (ultraviolet curable resin), thermosetting resin, electron beam curing resin, room temperature curing resin, thermoplastic resin, etc.
  • polyethylene resin polyvinyl chloride resin, polyvinylidene chloride resin, polyvinyl alcohol resin, polystyrene resin, polypropylene resin, ethylene vinyl acetate copolymer, polyester resin, polyethylene terephthalate resin, fluorine resin, polycarbonate resin, acrylic resin And polyvinyl butyral resins and the like.
  • a metal alkoxide is also possible as a binder component.
  • the metal alkoxide include alkoxides of Si, Ti, Al, Zr and the like. The binder using these metal alkoxides can form an oxide film by hydrolysis and condensation polymerization by heating or the like.
  • the light-to-heat conversion layer according to the present invention can generate heat only at a desired location with high accuracy. As a result, it is considered to be applicable in the field to a wide range of electronics, medicine, agriculture, machinery, etc.
  • 1) the ratio of the infrared absorption particles to the binder component, 2) the average particle diameter of the infrared absorption particles in the light-to-heat conversion layer The thickness of the light-to-heat conversion layer, and 5) the method for producing the light-to-heat conversion layer will be described in this order.
  • the ratio of infrared absorbing particles contained in the light-to-heat conversion layer to the binder component is not particularly limited, and the thickness of the light-to-heat conversion layer or the light-to-heat conversion layer is required It can be arbitrarily selected according to the absorption characteristics of the laser beam and the like, and is not particularly limited. However, for example, when using the light-to-heat conversion layer in various applications, it is preferable to select the ratio of the infrared absorbing particles and the binder component so that the light-to-heat conversion layer can maintain the form of a film.
  • the light-to-heat conversion layer may further contain any component other than the above-described infrared absorbing particles and the binder component. Further, as described later, when forming the light-to-heat conversion layer, for example, a dispersant, a solvent, and the like can be added to the ink serving as the raw material of the light-to-heat conversion layer, these components remain, and the light-to-heat conversion layer is formed. It may be included.
  • the average particle diameter of infrared absorbing particles in the light-to-heat conversion layer of the infrared absorbing particles is selected according to the degree of transparency required for the light-to-heat conversion layer, the degree of absorption of laser light, etc. Do.
  • the infrared absorbing particles are preferably fine particles.
  • the average particle diameter of the infrared absorbing particles is preferably 100 nm or less, and more preferably 10 nm to 100 nm. This is because, when the average particle diameter of the infrared absorbing particles is 10 nm or more, for example, when applied to a donor sheet, laser light can be sufficiently absorbed.
  • the infrared absorbing particles can be stably dispersed when mixed with, for example, a dispersing agent, a solvent, etc., and coated on the substrate particularly uniformly. It is because you can do it. As a result, it is possible to maintain the transparency of light in the visible region and to enhance the transparency of the light-to-heat conversion layer.
  • the average particle size of the infrared absorbing particles is 10 nm or more and 100 nm or less, and the infrared absorbing particles are not aggregated, the light is not scattered by geometric scattering or Mie scattering, thereby reducing the haze. .
  • the light-to-heat conversion layer according to the present invention does not scatter light, so that the accuracy of the processing position etc. is improved. It is because it is preferable from a viewpoint of aiming at the increase in the transmittance
  • the scattered light is reduced in proportion to the sixth power of the particle diameter, so the scattering is reduced as the dispersed particle diameter is reduced, and the transparency is improved. Therefore, when the average particle diameter is 100 nm or less, the scattered light is extremely reduced, which is preferable.
  • the light-to-heat conversion layer according to the present invention can be applied to a wide range of fields, such as electronics, medical care, agriculture, machinery, etc., since it becomes possible to generate heat only at desired places with high position accuracy Conceivable.
  • fields such as electronics, medical care, agriculture, machinery, etc.
  • curing or thermal transfer of a thermosetting resin becomes possible.
  • the light-to-heat conversion layer of the present invention is applied to a donor sheet used for producing an organic electroluminescent device or the like by irradiation of a laser beam, visible light can improve transfer accuracy due to low haze.
  • Permeable donor sheets can be produced.
  • the haze of the light-to-heat conversion layer is preferably 3% or less.
  • the photothermal conversion layer according to the present invention preferably has a solar radiation transmissivity of 45% or less. If the solar light transmittance of the light-to-heat conversion layer is 45% or less, sufficient heat generation can be obtained in the light-to-heat conversion layer. This is because, for example, when a transfer layer is transferred on a donor sheet, a laser beam having a near infrared region, in particular, a wavelength near 1000 nm is used. For this reason, it is preferable that the light-to-heat conversion layer has a high light absorptivity in the region. That is, it is preferable that the light transmittance of the region concerned is low.
  • the light-to-heat conversion layer is preferable because it can sufficiently absorb light near a wavelength of 1000 nm and generate heat.
  • the transmittance at a wavelength of 1000 nm of the photothermal conversion layer is preferably 20% or less, and more preferably 15% or less.
  • the thickness of the light-to-heat conversion layer is determined by the infrared absorption characteristics of the infrared-absorbing particles added to the light-to-heat conversion layer, the packing density of the infrared-absorbing particles in the light-to-heat conversion layer Select according to
  • the thickness of the photothermal conversion layer according to the present invention is, for example, preferably 5 ⁇ m or less, and more preferably 3 ⁇ m or less. This is because when the thickness of the light-to-heat conversion layer is increased, the heat generated when the light-to-heat conversion layer is irradiated with the laser light is easily diffused. For example, when it is used as a light-to-heat conversion layer of a donor sheet, if the thickness of the light-to-heat conversion layer is 5 ⁇ m or less, heat does not diffuse in the in-plane direction from the point irradiated with laser light; In this case, the transfer layer is not peeled off and transferred, which is preferable.
  • the lower limit of the thickness of the light-to-heat conversion layer is not particularly limited, and can be selected arbitrarily according to the infrared absorption characteristics of the infrared absorbing particles.
  • the thickness of the light-to-heat conversion layer is preferably 500 nm or more, and more preferably 1 ⁇ m or more. This is because if the thickness of the light-to-heat conversion layer is 500 nm or more, the amount of heat generated upon irradiation with laser light can be secured, so the density of the infrared absorbing particles dispersed in the light-to-heat conversion layer is not excessively increased. This is because it is easy to maintain the shape of the light-to-heat conversion layer.
  • the above-described light-to-heat conversion layer is prepared, for example, by mixing the above-described composite tungsten oxide fine particle dispersion and the binder component to produce an ink, applying the ink on a substrate, drying the applied ink, and drying. It can be formed by curing the cured ink. That is, the ink contains infrared absorbing particles, a dispersant, a solvent, and a binder component.
  • coats the ink containing infrared rays absorption particle, a dispersing agent, a solvent, and a binder component there exists a film base material, for example.
  • the said base material can also be comprised only from a film base material, what formed arbitrary layers on the film base material can also be used. Therefore, application of the ink containing the infrared absorbing particles, the dispersant, the solvent, and the binder component on the substrate is not limited to the case where the ink is directly applied on the film substrate.
  • the intermediate layer etc. which are mentioned later are formed on a film substrate, and the ink concerning the upper layer concerned concerned formed on a film substrate is applied is also included.
  • the light-to-heat conversion layer can be formed by drying and curing the ink after the application of the ink.
  • the composite tungsten oxide fine particle dispersion described above and a binder component can be mixed to produce an ink for forming a light-to-heat conversion layer.
  • it may be mixed to such an extent that both are sufficiently mixed.
  • the method of mixing the dispersion and the binder component is also not particularly limited.
  • the dispersion and the binder component are mixed using the same means as the pulverizing and dispersing means used in preparing the dispersion. You can also However, when preparing the ink as described above, the dispersion liquid and the binder component may be mixed to such an extent that they are sufficiently mixed, and the mixing time can be shorter than when the dispersion liquid is prepared.
  • the lattice constant of the composite tungsten oxide fine particles at the completion of the mixing may be such that the a axis is 7.3850 ⁇ or more and 7.4186 ⁇ or less and the c axis is 7.5600 ⁇ or more and 7.6240 ⁇ or less.
  • the method of coating the ink on the substrate is not particularly limited, and can be coated by, for example, a bar coating method, a gravure coating method, a spray coating method, a dip coating method, or the like.
  • it does not specifically limit as a film base material, According to a use, arbitrary film base materials can be used.
  • the same film substrate as the donor sheet described later can also be used.
  • the method of drying the ink is not particularly limited.
  • the heating temperature can be selected and dried according to the boiling point of the solvent used.
  • the method of curing the ink dried in the drying step is not particularly limited. It can be cured by a method according to the resin of the binder component and the like.
  • the binder component is an ultraviolet curable resin
  • it can be cured by irradiating it with ultraviolet light.
  • curing can be performed by raising the temperature to the curing temperature.
  • the photothermal conversion layer according to the present invention can be obtained by the above steps.
  • the light-to-heat conversion layer according to the present invention can be used in various applications where a light-to-heat conversion layer that absorbs laser light and generates heat is required.
  • the use thereof is not particularly limited, but can be suitably used, for example, as a light-to-heat conversion layer of a donor sheet, thermal paper for a thermal printer, or an ink ribbon for a thermal transfer printer.
  • the film base 21 is a layer that supports the light-to-heat conversion layer 22 and the transferred layer 23. And when irradiating a laser beam with respect to the donor sheet 20, the laser beam of wavelength 1000nm vicinity will be irradiated from the other surface 21B side of the film base 21, for example. For this reason, it is preferable that the film base 21 is excellent particularly in the near-infrared light transmittance so that the laser light can be transmitted to the light-to-heat conversion layer 22.
  • the film substrate 21 is preferably excellent in visible light transmittance so that defects such as foreign matter and coating unevenness in the donor sheet 20 can be detected visually or by a visible light sensor or the like.
  • a material excellent in the transmittance of visible light and light in the near infrared region can be preferably used.
  • the thickness of the film substrate 21 is not particularly limited, and may be arbitrarily selected according to the type of the material used for the film substrate 21 and the transmittance of visible light and near infrared light required for the donor sheet, etc. can do.
  • the thickness of the film substrate 21 is preferably, for example, 1 ⁇ m or more and 200 ⁇ m or less, and more preferably 2 ⁇ m or more and 50 ⁇ m or less. This is because by setting the thickness of the film substrate 21 to 200 ⁇ m or less, the transmittance of visible light and near infrared light can be enhanced, which is preferable. Further, by setting the thickness of the film substrate 21 to 1 ⁇ m or more, the light-to-heat conversion layer 22 and the like formed on the film substrate 21 can be supported, and breakage of the donor sheet 20 can be particularly prevented.
  • the transferred layer according to the present invention will be described with reference to FIG. 3 which is an explanatory view of a cross-sectional configuration example of a donor sheet according to the present invention.
  • the transferred layer 23 is a layer which is peeled off from the donor sheet 20 by irradiating the donor sheet 20 with laser light and is transferred, and the configuration thereof is not particularly limited. It can be any layer.
  • the example to which the to-be-transferred layer 23 was comprised by one layer is shown in FIG. 3, it is not limited to the form which concerns, For example, the to-be-transferred layer 23 which consists of two or more layers can also be comprised.
  • the donor sheet 20 can be used, for example, in forming an organic electroluminescent device.
  • the transferred layer 23 includes one or more layers selected from, for example, a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, a blocking layer, an electron transport layer and the like constituting an organic electroluminescent device. It can be configured as follows.
  • the formation method of the to-be-transferred layer 23 is not specifically limited, According to the kind of material which comprises a layer, it can form by arbitrary methods.
  • the donor sheet 20 is not limited to the case of forming an organic electroluminescent element, but may be various electronic devices such as electronic circuits, resistors, capacitors, diodes, rectifiers, memory elements, transistors, etc., various optical devices such as optical waveguides, It can also be used when forming. Therefore, the transferred layer 23 can have an arbitrary configuration according to the application.
  • the example of 1 structure of a donor sheet was demonstrated so far, the structure of a donor sheet is not limited to the form which concerns, A further arbitrary layer can also be added.
  • an intermediate layer may be provided between the light-to-heat conversion layer 22 and the transferred layer 23 to suppress damage and contamination of the transferred portion of the transferred layer 23.
  • the configuration of the intermediate layer is not particularly limited, and may be, for example, a polymer film, a metal layer, an inorganic layer (for example, an inorganic oxide layer such as silica or titania), an organic / inorganic composite layer, or the like.
  • an inorganic layer for example, an inorganic oxide layer such as silica or titania
  • an organic / inorganic composite layer or the like.
  • the transfer layer 23 may be disposed on one surface 21A of the film substrate 21, and the light-to-heat conversion layer 22 may be disposed on the other surface 21B.
  • the donor sheet according to the present invention has the light-to-heat conversion layer according to the present invention described above.
  • the light-to-heat conversion layer according to the present invention has a high visible light transmittance, defects in the donor sheet are detected by visual observation or visible light sensor even through the light-to-heat conversion layer, and the defective donor sheet is inspected by inspection. It can be removed. For this reason, it is possible to increase the yield when an electronic device such as an organic electroluminescent element or an optical device is manufactured using the donor sheet according to the present invention.
  • the light-to-heat conversion layer according to the present invention has a low haze
  • the light-to-heat conversion layer according to the present invention is a donor sheet capable of improving the position accuracy in transfer of an organic electroluminescent element or the like by laser light irradiation. is there.
  • Example 1 (Preparation of light-to-heat conversion layer)
  • the photothermal conversion layer was produced according to the following procedure. A solution was obtained by dissolving 7.43 kg of cesium carbonate (Cs 2 CO 3 ) in 6.70 kg of water. The solution was added to 34.57 kg of tungstic acid (H 2 WO 4 ), sufficiently stirred and mixed, and then dried with stirring (the molar ratio of W to Cs is equivalent to 1: 0.33). The dried product was heated while supplying 5% by volume of H 2 gas using N 2 gas as a carrier, and baked at a temperature of 800 ° C. for 5.5 hours, and then the supplied gas was switched to only N 2 gas. The mixture was cooled to room temperature to obtain composite tungsten oxide particles.
  • Cs 2 CO 3 cesium carbonate
  • H 2 WO 4 tungstic acid
  • Acrylic polymer dispersant (acrylic dispersant having an amine value of 48 mg KOH / g and decomposition temperature of 250 ° C.) containing 10% by mass of the composite tungsten oxide particles and an amine-containing functional group (hereinafter referred to as “dispersant” Described as a)) 10% by mass and 80% by mass of toluene were weighed and loaded in a paint shaker (manufactured by Asada Iron Works Co., Ltd.) containing 0.3 mm ⁇ ZrO 2 beads and ground and dispersed for 10 hours Thus, a composite tungsten oxide fine particle dispersion according to Example 1 was prepared. At this time, pulverization / dispersion treatment was performed using 300 parts by mass of 0.3 mm ⁇ ZrO 2 beads with respect to 100 parts by mass of the mixture.
  • the dispersion particle diameter of the composite tungsten oxide fine particles in the composite tungsten oxide fine particle dispersion is observed for fluctuation of scattered light of laser using ELS-8000 manufactured by Otsuka Electronics Co., Ltd., and a dynamic light scattering method
  • the autocorrelation function was determined by (photon correlation method), and the average particle size (hydrodynamic size) was calculated by the cumulant method, which was 70 nm.
  • the particle refractive index was set to 1.81, and the particle shape was non-spherical.
  • the background was measured using toluene, and the solvent refractive index was 1.50.
  • the visible light transmittance and the solar radiation transmittance were measured as optical properties of the composite tungsten oxide fine particle dispersion, using a spectrophotometer U-4100 manufactured by Hitachi, Ltd. based on JIS R 3106 (1998). did.
  • the measurement was performed by filling a solution obtained by diluting the composite tungsten oxide fine particle dispersion with toluene in a measurement glass cell of a spectrophotometer.
  • the dilution with toluene was performed such that the visible light transmittance of the composite tungsten oxide fine particle dispersion after dilution was about 70%.
  • the incident direction of light of the spectrophotometer was a direction perpendicular to the measurement glass cell.
  • the light transmittance was measured also in the blank liquid which put only toluene which is a dilution solvent to the glass cell for the measurement, and made the measurement result the baseline of the light transmittance.
  • the visible light transmittance was 70.2%
  • the solar radiation transmittance was 34.9%.
  • a UV curable resin and methyl isobutyl ketone are mixed with the obtained composite tungsten oxide fine particle dispersion to prepare an ink according to Example 1, and a bar coater (IMC-made by Imoto Machinery Co., Ltd.) is produced on a PET film of 50 ⁇ m
  • the coated film was formed by coating at 700) to form a coated film, and the coated film was dried at 80 ° C. for 60 seconds to evaporate the solvent. Thereafter, the coated film was cured by ultraviolet irradiation to prepare a light-to-heat conversion layer containing composite tungsten oxide fine particles on a film substrate.
  • the average particle diameter of the composite tungsten oxide fine particles dispersed in the light-to-heat conversion layer was 25 nm as calculated by the image processing apparatus using a transmission electron microscope image. Moreover, the film thickness of the light-to-heat conversion layer was 2.5 ⁇ m from the TEM image.
  • the optical properties of the sheet comprising the light-to-heat conversion layer were measured at intervals of 5 nm in a wavelength range of 200 nm to 2600 nm by a spectrophotometer (U-4100 manufactured by Hitachi, Ltd.).
  • the optical characteristics of the film substrate alone were also measured in the same manner, and the optical characteristics of the light-to-heat conversion layer were calculated by subtracting the above-mentioned measured values.
  • the visible light transmittance is 69.8% and the solar radiation transmittance is The 35.9% transmittance at a wavelength of 1000 nm was 5%.
  • the haze of the sheet comprising the light-to-heat conversion layer was evaluated based on JIS K 7105 using a haze meter (HM-150, manufactured by Murakami Color Research Laboratory), and it was 0.9%. As a result of similarly measuring a haze also about the used film base material, it was 0.8%. From this, it was found that the haze from the light-to-heat conversion layer was almost completely absent, and the composite tungsten oxide fine particles in the light-to-heat conversion layer were not aggregated. The evaluation results are shown in Table 2.
  • a transfer layer was further formed on the produced light-to-heat conversion layer to form a donor sheet.
  • the donor sheet was formed to have the structure described in FIG. Specifically, the transfer layer 23 was formed on the top surface of the light-to-heat conversion layer 22.
  • the electron transport layer was formed by depositing Alq 3 [tris (8-quinolinolato) aluminum (III)] by vapor deposition to a film thickness of 20 nm.
  • the organic light emitting layer is formed of a blue light emitting guest material, ADN (anthracene dinaphytyl) which is an electron transporting host material, and a blue light emitting guest material, 4,4′-bis [2 ⁇ ⁇ 4 ⁇ (N, N ⁇ diphenylamino)]
  • a material in which 2.5 wt% of phenyl ⁇ vinyl] biphenyl (DPAVBi) was mixed was deposited by vapor deposition to a film thickness of about 25 nm.
  • the hole transport layer was formed to a film thickness of 30 nm by depositing ⁇ -NPD [4,4-bis (N-1-naphthyl (N-phenylamino) biphenyl]] by vapor deposition.
  • the hole injection layer was formed by depositing m-MTDATA [4,4,4-tris (3-methylphenylphenylamino) triphenylamine] by a vapor deposition method, and the film thickness was 10 nm.
  • the to-be-transferred layer 23 was visually observed from the film base material side, and the state was confirmed.
  • Example 2 In Example 1, tungstic acid and cesium carbonate, or an ammonium metatungstate aqueous solution (50 mass% in terms of WO 3 ) and cesium carbonate, and the molar ratio of W to Cs is 1: 0.20 The same operation as in Example 1 was carried out except that a predetermined amount was weighed so as to be .37. Then, composite tungsten oxide particles and composite tungsten oxide fine particle dispersions according to Examples 2 to 11 were obtained. Furthermore, using the composite tungsten oxide fine particle dispersion, a light-to-heat conversion layer and a donor sheet were obtained, and these characteristics were measured.
  • Example 1 the same film thickness as in Example 1 was obtained by adjusting the compounding ratio of the composite tungsten oxide fine particle dispersion according to Examples 2 to 11, the ultraviolet curable resin used in Example 1, and methyl isobutyl ketone A photothermal conversion layer having a transmittance of 5% at a wavelength of 1000 nm was formed. In each of the composite tungsten oxide fine particle samples, a hexagonal crystal structure was confirmed. Tables 1 and 2 show synthesis conditions, production conditions and measurement results according to Examples 2 to 11.
  • Example 1 is the same as Example 1 except that the composite tungsten oxide particles described in Example 1 are fired at a temperature of 550 ° C. for 9.0 hours while supplying 5% H 2 gas using N 2 gas as a carrier. It operated similarly. And the composite tungsten oxide particles and the composite tungsten oxide fine particle dispersion according to Example 12 were obtained. Furthermore, using the composite tungsten oxide fine particle dispersion, a light-to-heat conversion layer and a donor sheet were obtained, and these characteristics were measured.
  • Example 12 the compounding ratio of the composite tungsten oxide fine particle dispersion according to Example 12, the ultraviolet curable resin used in Example 1, and the methyl isobutyl ketone is adjusted, and the same film thickness as in Example 1 is 2.5 ⁇ m.
  • a hexagonal crystal structure was confirmed.
  • the synthesis conditions, the production conditions and the measurement results according to Example 12 are shown in Tables 1 and 2.
  • Examples 13 to 17 In 6.70 kg of water, 5.56 kg of rubidium carbonate (Rb 2 CO 3 ) was dissolved to obtain a solution. The solution was added to 36.44 kg of tungstic acid (H 2 WO 4 ), sufficiently stirred and mixed, and then dried with stirring to obtain a dried product according to Example 13 (molar ratio between W and Rb Is equivalent to 1: 0.33.).
  • Rb 2 CO 3 rubidium carbonate
  • a solution was obtained by dissolving 0.709 kg of cesium carbonate (Cs 2 CO 3 ) and 5.03 kg of rubidium carbonate (Rb 2 CO 3 ) in 6.70 kg of water.
  • the solution was added to 36.26 kg of tungstic acid (H 2 WO 4 ), sufficiently stirred and mixed, and then dried with stirring to obtain a dried product according to Example 14 (molar ratio of W to Cs Is equivalent to 1: 0.03, and the molar ratio of W to Rb is equivalent to 1: 0.30).
  • a solution was obtained by dissolving 4.60 kg of cesium carbonate (Cs 2 CO 3 ) and 2.12 kg of rubidium carbonate (Rb 2 CO 3 ) in 6.70 kg of water. The solution was added to 35.28 kg of tungstic acid (H 2 WO 4 ), sufficiently stirred and mixed, and then dried with stirring to obtain a dried product according to Example 15 (molar ratio of W to Cs The molar ratio of W to Rb is equivalent to 0.13.
  • a solution was obtained by dissolving 5.71 kg of cesium carbonate (Cs 2 CO 3 ) and 1.29 kg of rubidium carbonate (Rb 2 CO 3 ) in 6.70 kg of water. The solution was added to 35.00 kg of tungstic acid (H 2 WO 4 ), sufficiently stirred and mixed, and then dried with stirring to obtain a dried product according to Example 16 (molar ratio of W to Cs) Is equivalent to 1: 0.25, and the molar ratio of W to Rb is equivalent to 1: 0.08).
  • Cs 2 CO 3 cesium carbonate
  • Rb 2 CO 3 rubidium carbonate
  • a solution was obtained by dissolving 6.79 kg of cesium carbonate (Cs 2 CO 3 ) and 0.481 kg of rubidium carbonate (Rb 2 CO 3 ) in 6.70 kg of water. The solution was added to 34.73 kg of tungstic acid (H 2 WO 4 ), sufficiently stirred and mixed, and then dried with stirring to obtain a dried product according to Example 17 (molar ratio of W to Cs The molar ratio of W to Rb is equivalent to 1: 0.03.
  • the dried products according to Examples 13 to 17 are heated while supplying 5% H 2 gas using N 2 gas as a carrier and calcined at a temperature of 800 ° C. for 5.5 hours, and then the supplied gas is N 2 Only the gas was switched to the room temperature, and composite tungsten oxide particles according to Examples 13 to 17 were obtained.
  • a composite according to Examples 13 to 17 operates in the same manner as Example 1, except that the composite tungsten oxide particles according to Examples 13 to 17 are used instead of the composite tungsten oxide particles according to Example 1.
  • a tungsten oxide fine particle dispersion was obtained. Furthermore, using the composite tungsten oxide fine particle dispersion, a light-to-heat conversion layer and a donor sheet were obtained, and these characteristics were measured. At this time, the same film thickness as in Example 1 was obtained by adjusting the compounding ratio of the composite tungsten oxide fine particle dispersion according to Examples 13 to 17, the ultraviolet curable resin used in Example 1, and methyl isobutyl ketone. A photothermal conversion layer having a transmittance of 5% at a wavelength of 1000 nm was formed. In each of the composite tungsten oxide fine particle samples, a hexagonal crystal structure was confirmed. The synthesis conditions, the production conditions and the measurement results according to Examples 13 to 17 are shown in Tables 1 and 2.
  • Example 18 In the method for producing a photothermal conversion layer described in Example 1, the same operation as in Example 1 is carried out except that the film thickness of the photothermal conversion layer is 3.0 ⁇ m, and the photothermal conversion layer and the donor sheet according to Example 18 I got The synthesis conditions, the production conditions, and the measurement results according to Example 18 are shown in Tables 1 and 2.
  • Example 1 the molar ratio of W and Cs of tungstic acid and cesium carbonate is 1: 0.11 (comparative example 1), 1: 0.15 (comparative example 2), 1: 0.39 (comparative example) The same operation as in Example 1 was carried out except that a predetermined amount was measured so as to be 3). Then, a composite tungsten oxide fine particle dispersion according to Comparative Examples 1 to 3 was obtained. Furthermore, using the composite tungsten oxide fine particle dispersion, a light-to-heat conversion layer and a donor sheet were obtained, and these characteristics were measured. In each of the composite tungsten oxide fine particle samples, a hexagonal crystal structure was confirmed. Tables 3 and 4 show the synthesis conditions, the production conditions and the measurement results according to Comparative Examples 1 to 3.
  • Example 1 the same film thickness as in Example 1 was obtained by adjusting the compounding ratio of the composite tungsten oxide fine particle dispersion according to Comparative Examples 1 to 3, the ultraviolet curable resin used in Example 1, and methyl isobutyl ketone.
  • the optical characteristics of the photothermal conversion layers according to Comparative Examples 1 to 3 according to Comparative Examples 1 to 3 in which the light transmittance at a wavelength of 1000 nm is 5% and the film thickness is 2.5 ⁇ m are measured.
  • the visible light transmittance is 26.3%, the solar radiation transmittance is 13.1%, the haze is 5.4%, and in the case of Comparative Example 2, the visible light transmittance is 27.7%, the solar radiation transmittance is 13.2%, the haze is 5.2%, and in the case of Comparative Example 3, the visible light transmittance is 28.8%, the solar radiation transmittance is 12.9%, the haze is 4.8%, and visual confirmation It turned out that it was a thing which can not be said that it was transparent.
  • Example 1 predetermined amounts of tungstic acid and cesium carbonate are weighed so that the molar ratio of W and Cs is 1: 0.21 (Comparative Example 4), 1: 0.23 (Comparative Example 5), The procedure of Example 1 was repeated except that the firing was performed at a temperature of 400 ° C. for 5.5 hours. And the composite tungsten oxide particles and the composite tungsten oxide fine particle dispersion according to Comparative Examples 4 and 5 were obtained. Furthermore, using the composite tungsten oxide fine particle dispersion, a light-to-heat conversion layer and a donor sheet were obtained, and these characteristics were measured.
  • Example 1 was repeated except that in the production of the composite tungsten oxide particle dispersion according to Example 1, the rotation speed of the paint shaker was 0.8 times that of Example 1, and that the grinding and dispersion treatment was performed for 100 hours. It operated similarly. And the composite tungsten oxide fine particle dispersion liquid which concerns on the comparative example 6 was obtained. Furthermore, in the same manner as in Example 1, a photothermal conversion layer and a donor sheet were obtained, and their characteristics were measured. At this time, the compounding ratio of the composite tungsten oxide fine particle dispersion according to Comparative Example 6, the ultraviolet curable resin used in Example 1, and methyl isobutyl ketone is adjusted, and the same film thickness as in Example 1 is 2.5 ⁇ m.
  • the light-to-heat conversion layer having a transmittance of 5% at a wavelength of 1000 nm was formed.
  • a hexagonal crystal structure was confirmed.
  • Tables 3 and 4 show synthesis conditions, manufacturing conditions, and measurement results according to Comparative Example 6.
  • Example 6 is the same as example 1 except that in the production of composite tungsten oxide particles according to example 1, baking is performed at a temperature of 440 ° C. for 5.5 hours while supplying 3 vol% H 2 gas using N 2 gas as a carrier. It operated to. And the composite tungsten oxide particle and composite tungsten oxide fine particle dispersion liquid which concern on the comparative example 7 were obtained. Furthermore, in the same manner as in Example 1, a photothermal conversion layer and a donor sheet were obtained, and their characteristics were measured.
  • Example 1 the same film thickness as in Example 1 is adjusted to 2.5 ⁇ m by adjusting the compounding ratio of the composite tungsten oxide fine particle dispersion according to Comparative Example 7, the ultraviolet curable resin used in Example 1, and methyl isobutyl ketone.
  • Tables 3 and 4 show the synthesis conditions, the production conditions and the measurement results according to Comparative Example 7.
  • Comparative Example 8 In the production of the composite tungsten oxide fine particle dispersion according to Example 1, 10% by mass of the composite tungsten oxide particles, 10% by mass of the dispersant a, and 80% by mass of toluene are weighed, and ultrasonic vibration is performed for 10 minutes. A composite tungsten oxide fine particle dispersion liquid according to Comparative Example 8 was obtained in the same manner as in Example 1 except for mixing. That is, the composite tungsten oxide fine particles contained in the composite tungsten oxide fine particle dispersion according to Comparative Example 8 are not pulverized. Furthermore, in the same manner as in Example 1, a photothermal conversion layer and a donor sheet were obtained, and their characteristics were measured.
  • Example 1 the same film thickness as in Example 1 is adjusted to 2.5 ⁇ m by adjusting the compounding ratio of the composite tungsten oxide fine particle dispersion according to Comparative Example 8, the ultraviolet curing resin used in Example 1, and methyl isobutyl ketone.
  • Tables 3 and 4 show the synthesis conditions, the production conditions and the measurement results according to Comparative Example 8.
  • Comparative Example 9 In the pulverization / dispersion treatment of the composite tungsten oxide particles according to the first embodiment, the rotation speed of the paint shaker is 1.15 times that of the first embodiment, and the pulverization / dispersion treatment is performed for 25 hours. It operated similarly. And the composite tungsten oxide fine particle dispersion liquid which concerns on the comparative example 9 was obtained. Furthermore, in the same manner as in Example 1, a photothermal conversion layer and a donor sheet were obtained, and their characteristics were measured. At this time, the same film thickness as in Example 1 is adjusted to 2.5 ⁇ m by adjusting the compounding ratio of the composite tungsten oxide fine particle dispersion according to Comparative Example 9, the ultraviolet curable resin used in Example 1, and methyl isobutyl ketone.
  • the light-to-heat conversion layer having a transmittance of 5% at a wavelength of 1000 nm was formed.
  • a hexagonal crystal structure was confirmed.
  • Tables 3 and 4 show the synthesis conditions, the production conditions and the measurement results according to Comparative Example 9.
  • Comparative Example 10 The infrared absorbing particles were changed from the composite tungsten oxide fine particles to carbon black to prepare a photothermal conversion layer and a donor sheet.
  • a dispersion was prepared by grinding and dispersing carbon black (BET specific surface area: 300 m 2 / g), a dispersing agent, and a solvent. The dispersion contains 10% by mass of carbon black.
  • the same dispersant a as in Example 1 was used as the dispersant, and it was weighed so that the proportion in the dispersion became 5% by weight.
  • As a solvent methyl isobutyl ketone was used, and it weighed so that the ratio in a dispersion liquid might be 85 weight%.
  • the obtained dispersion according to Comparative Example 10 and a binder component were mixed to prepare an ink.
  • the same UV-3701 as in Example 1 was used as a binder component.
  • 100 parts by mass of UV-3701 was mixed with 100 parts by mass of the dispersion according to Comparative Example 5 to obtain an ink according to Comparative Example 10 containing carbon black particles.
  • the obtained ink (coating liquid) was coated on a 50 ⁇ m-thick PET film using a bar coater to form a coated film. And it dried similarly to Example 1, irradiated with an ultraviolet-ray and hardened
  • the light-to-heat conversion layer produced from the composite tungsten oxide fine particles according to Examples 1 to 17 has excellent infrared absorption characteristics compared to the composite tungsten oxide fine particles of Comparative Examples 1 to 10. Demonstrated.
  • the composite tungsten oxide fine particles contained in the dispersions according to Examples 1 to 17 have lattice constants of 7.3850 ⁇ to 7.4186 ⁇ in the a axis and 7.5600 ⁇ to 7.6240 ⁇ in the c axis. It was a composite tungsten oxide fine particle having a particle diameter of 100 nm or less.
  • the average particle diameter and the crystallite diameter of the composite tungsten oxide fine particles in the light-to-heat conversion layer are substantially the same in the examples, it is considered to be single crystal composite tungsten oxide fine particles.
  • the above-mentioned lattice constant range or particle diameter range was out of range.
  • the state of the transferred layer could be visually confirmed from the film substrate side, but for each comparative example, the transparency of the light-to-heat conversion layer was not sufficient and the state of the transferred layer could not be confirmed visually.

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PCT/JP2018/034176 2017-09-14 2018-09-14 光熱変換層、当該光熱変換層を用いたドナーシート、およびそれらの製造方法 WO2019054480A1 (ja)

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CA3086138A CA3086138A1 (en) 2017-09-14 2018-09-14 Light to heat conversion layer, donor sheet using light to heat conversion layer, and method for producing light to heat conversion layer
AU2018331911A AU2018331911B2 (en) 2017-09-14 2018-09-14 Photothermal conversion layer, donor sheet using photothermal conversion layer, and method for producing layer and sheet
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EP18856184.9A EP3683604A4 (en) 2017-09-14 2018-09-14 PHOTOTHERMAL CONVERSION LAYER, DONOR SHEET USING A PHOTOTHERMAL CONVERSION LAYER, AND LAYER AND SHEET PRODUCTION PROCESS
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US16/647,600 US11912054B2 (en) 2017-09-14 2018-09-14 Light to heat conversion layer, donor sheet using light to heat conversion layer, and method for producing light to heat conversion layer
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